5-C1-4 alkoxy-2-C1-2 alkyl-2&#39;,4&#39;-dinitro-6&#39;-halo-4-substituted amino-azobenzenes

ABSTRACT

Compounds of the formula ##STR1## wherein R 1  is nitro or cyano; 
     R 2  is cyano or halo; 
     R 3  is C 1-4  alkyl; 
     R 4  is methyl or ethyl; 
     R 5  is C 1-8  alkyl; and 
     R 6  is --CH 2  CHOHCH 2  O(CH 2  CH 2  O) a  R 7 , --CH 2  CHOHC 6  H 5 , --CH(C 6  H 5 )CH 2  OH; --(CH 2 ) n  O--CO--NHR 3 , --CH 2  CH(R 4 )--O--CO--NHR 3  ; --(CH 2 ) n  --O--CO--R 3 , --CH 2  CH(R 4 )--O--CO--R 3  or C 2-4  hydroxyalkyl, with the provisos that R 6  may be any of the last three groups only when R 1  and R 2  are both cyano and that R 6  may be C 2-4  hydroxyalkyl also when R 5  is C 1-2  alkyl, 
     wherein 
     R 7  is phenyl; phenyl substituted by 1 or 2 substituents independently selected from hydroxy, chloro, bromo, methyl and C 1-4  alkoxy; benzyl; benzyl substituted by 1 or 2 substituents independently selected from hydroxy, chloro, bromo, methyl and C 1-4  alkoxy; allyl; haloalkyl; propyn-2-yl or halopropyn-2-yl, with the proviso that R 7  may be allyl, haloallyl, propyn-2-yl or halopropyn-2-yl only when a is 0; 
     a is 0 or 1; and 
     n is 2 or 3, 
     processes for their preparation and their use for dyeing and printing textiles comprising synthetic or semi-synthetic, hydrophobic, high molecular weight materials, e.g., linear aromatic polyester, cellulose 21/2 acetate, cellulose triacetate and synthetic polyamides, by, for example, the rapid dyeing procedure.

The invention relates to disperse dyes and in particular to their use inrapid dyeing.

The invention provides compounds of formula I ##STR2## in which R₁ is--NO₂ or --CN;

R₂ is --CN or halogen;

R₃ is C₁₋₄ alkyl;

R₄ is methyl or ethyl;

R₅ is C₁₋₈ alkyl; and

R₆ is --CH₂ CHOHCH₂ O(CH₂ CH₂ O)_(a) R₇ ; --CH₂ CHOHC₆ H₅ ; --CH(C₆H₅)CH₂ OH, --(CH₂)_(n) O--CO--NHR₃ or --CH₂ CH(R₄)--O--CO--NHR₃ ;

or when both R₁ and R₂ are --CN, also --(CH₂)_(n) --O--CO--R₃, --CH₂CH(R₄)--O--CO--R₃ or a straight chain or branched C₂₋₄ -hydroxyalkylgroup;

or when R₅ is methyl or ethyl additionally linear or branched C₂₋₄hydroxy alkyl; and

R₇ is phenyl, unsubstituted or substituted by up to two groups selectedfrom --OH, Cl, Br, methyl and C₁₋₄ alkoxy; benzyl, unsubstituted orsubstituted by up to two groups selected from --OH, Cl, Br, methyl orC₁₋₄ alkoxy; and, when a is zero, R₇ is additionally allyl,unsubstituted or substituted by one halogen, or propyn-2-yl,unsubstituted or substituted by one halogen;

a is 0 or 1; and

n is 2 or 3.

Where a symbol appears more than once in a formula its significances areindependent of one another.

By the term "halogen" is meant F, Cl, Br and I, more preferably Cl andBr.

In R₆ preferred groups of linear and branched C₂₋₄ -hydroxyalkyl groupsare --CH₂ OHR₄ and --(CH₂)_(b) OH where b is 1, 2 or 3. Preferred C₁₋₄alkoxy groups are methoxy and ethoxy.

Preferably R₃ and R₄ are methyl.

Preferably R₅ is C₁₋₄ alkyl, more preferably C₁₋₃ alkyl, most preferablymethyl and ethyl.

Preferred compounds of formula I are of formula II, III or IV, ##STR3##in which R₁ and R₂ are defined above;

R₃ ' and R₄ ' are methyl;

R₅ ' is C₁₋₄ alkyl; and

R₆ ' is --CH₂ CHOHCH₂ O(CH₂ CH₂ O)_(a) R₇ '; or when R₁ and R₂ are --CN,additionally --CH₂ CHOHC₆ H₅, --CH(C₆ H₅)CH₂ OH, --CH₂ CH₂ OCOR₃, --CH₂CH₂ OCONHR₃ or linear or branched C₂₋₃ hydroxyalkyl or, when R₅ ismethyl or ethyl, additionally linear or branched C₂₋₃ hydroxyalkyl; and

R₇ ' is phenyl, unsubstituted or substituted by up to two groupsselected from --OH, Cl, Br, methyl and C₁₋₄ alkoxy; ##STR4## in whichR₃, R₄, R₅ ' are defined above; and

R₁ ' and R₂ ' are --CN;

R_(6a) is linear or branched C₂₋₃ hydroxyalkyl, --CH₂ CH₂ OCONHR₃, --CH₂CH(R₄)O--CONHR₃, --CH₂ CH₂ OCOR₃ ; --CH₂ CH(R₄)OCOR₃, --CH₂ CH(C₆ H₅)OHor --CH(C₆ H₅)CH₂ OH; ##STR5## in which R₃ and R₄ are defined above;

R_(1a) is NO₂ ;

R_(2a) is --CN, Cl or Br;

R₅ " is methyl or ethyl;

R_(6b) is linear or branched C₂₋₃ hydroxyalkyl orβ-hydroxy-γ-phenoxypropyl.

Preferably in compounds of formula II, R₆ ' is

    --CH.sub.2 CHOHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.a R.sub.7 ',

where a and R₇ ' are as defined above.

Preferably in compounds of formula III, R₃ and R₄ are methyl, R₅ ' isC₁₋₃ alkyl and R_(6a) is acetoxyethyl.

Preferably in compounds of formula IV R_(2a) is Cl or Br, R₃ and R₄ aremethyl, R₅ " is methyl or ethyl and R_(6b) is β-hydroxy-γ-phenoxypropyl.

Most preferred compounds of formula I are those in which R₁ is --NO₂, R₂is Cl or Br, R₃ and R₄ are methyl, R₅ is methyl or ethyl (preferablymethyl) and R₆ is --CH₂ CHOHCH₂ OC₆ H₅ or --CH₂ CH₂ OH.

The compounds of formula I may be prepared by reacting a diazotisedamine of formula V ##STR6## with a compound of formula VI ##STR7## inwhich R₁ -R₆ are defined above.

The compounds of formulae V and VI are known or may be made by knownmethods from known compounds.

Azo compounds of formula I in which R₁ and/or R₂ are cyano groups may beprepared from compounds of the formula ##STR8## in which R_(1b) is Cl,Br, I or --NO₂ ;

R_(2b) is Cl, Br or I; and

R₃ -R₆ are defined above;

by replacing the halogen of R_(2b) and R_(1b) (when present) with acyano group.

Cyano group exchange may be carried out by a variety of known cyanoexchange methods.

Dyeing preparations of the compounds of formula I may be formulated byknown methods, for example by grinding in the presence of a dispersingagent or a filling material. The preparation (which may be vacuum driedor atomised dried) can be used for dyeing, padding or printing with theaddition of water from a short or long dyebath.

The dyestuffs exhaust very well from aqueous suspensions on textilematerial of semi- or fully synthetic hydrophobic high molecular weightmaterial. The dyestuffs exhaust particularly well on textile materialformed from linear aromatic polyester or cellulose 21/2 acetate,cellulose triacetate or synthetic polyamides.

Dyeing and printing can be carried out according to the method ofBritish Pat. No. 1,114,433.

The compounds of formula I are useful in the so called "rapid dyeing"procedure, in particular for the rapid dyeing of polyester material. Inthis method the substrate is immersed in a dyebath in a dyeing apparatusand heated to 130° C. over a time period of 20-30 minutes and then ismaintained only for a further 20 minutes at this temperature.

The resulting dyeings show overall good fastnesses, in particular goodlight fastness, thermofixation fastness, sublimation fastness andpleating fastness.

The invention will now be illustrated by the following examples in whichall parts and percentages are by weight and all temperatures are in °C.

EXAMPLE 1

122 Parts of concentrated sulphuric acid and 35 parts of a 40%nitrosylsulphuric acid are mixed ensuring that the temperature of themixture does not exceed 20° C.

26.2 Parts of 2-bromo-4,6-dinitroaniline are added to the above mixtureand are stirred for 4 hours maintaining the temperature of the mixturebetween 15° and 20°. The solution is slowly added, whilst stirring andcooling at a temperature of -5° to 0°, to a solution of 30.1 parts ofN-methyl-N-(β-hydroxy-γ-phenoxypropyl)-2-methoxy-5-methylaniline, 50parts of sodium acetate in 500 parts of glacial acetic acid and 750parts of a mixture of water and ice. The temperature of the couplingreaction is maintained at 0° to 5° by the further addition of ice.

After coupling is completed the resulting dyestuff is filtered, washedwith slightly acidic and salt-free water and is stirred overnight into afresh amount of 3000 parts of water.

The mixture is then heated to 90° and maintained at this temperature for4 hours.

After filtration, washing, drying and recrystallisation, the dyestuff ofthe formula ##STR9## results. This dyestuff dyes polyester material anavy blue colour and gives good fastness properties. The dyestuff isalso very good in "rapid dyeing" processes.

EXAMPLE 2

To a mixture of 200 parts glacial acetic acid, 40 parts of sulphuricacid and 35 parts of nitrosylsulphuric acid formed below 10°, 24.2 partsof 2-bromo-4-nitro-6-cyanoaniline are added according to the method ofExample 1 and then the solution is added to a mixture of 26.5 parts ofN-propyl-N-(β-acetoxyethyl)-p-cresidine, 50 parts of sodium acetatedissolved in 500 parts of glacial acetic acid and 750 parts of a mixtureof water and ice, whereby coupling occurs whilst the reaction ismaintained at 0°-5° C.

After completion of the coupling the resulting dyestuff is filtered,washed with acid free water and stirred overnight in a fresh amount of3000 parts of water. The dyestuff is filtered, dried and recrystallisedfrom ethyl acetate, dissolved in 400 parts of dimethylformamide, reactedwith 9 parts of CuCN and stirred at 70° for 24 hours, whereby thereddish blue solution is converted to a greenish blue solution and thedyestuff precipitates in crystalline form. After cooling the reactionmass, the dyestuff is filtered, washed with water and stirred in a freshamount of 300 parts water, 10 parts of HCl (conc.) and 20 parts offerric chloride at room temperature for 1 hour. The dyestuff isfiltered, washed with water, dried and recrystallized from ethylacetate. The dyestuff of the formula ##STR10## that results dyespolyester a blue tone.

EXAMPLES 3 TO 103

Compounds of the formula ##STR11## are produced according to the methodof Example 1 or 2, in which R₁ to R₆ are given in the Table below

                                      TABLE                                       __________________________________________________________________________    EX.                                                                           NO. R.sub.5                                                                              R.sub.6                R.sub.3                                                                            R.sub.4                                                                            R.sub.1                                                                           R.sub.2                       __________________________________________________________________________    3   CH.sub.3                                                                             CH.sub.2 CH.sub.2 OH   CH.sub.3                                                                           CH.sub.3                                                                           NO.sub.2                                                                          Cl                            4   "      "                      "    "    "   I                             5   "      "                      "    "    "   Br                            6   "      "                      "    "    "   F                             7   C.sub.2 H.sub.5                                                                      "                      CH.sub.3                                                                           "    "   Br                            8   "      "                      "    "    "   Cl                            9   "      "                      C.sub.2 H.sub.5                                                                    "    "   Cl                            10  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.3  CH.sub.3                                                                           "    "   Br                            11  C.sub.2 H.sub.5                                                                      "                      "    "    "   Cl                            12  "      CH.sub.2 CHOHC.sub.2 H.sub.5                                                                         "    "    "   Br                            13  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                                               "    "    "   Cl                            14  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.44-Cl                                                           "    "    "   Br                            15  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.43-OH                                                           "    "    "   Br                            16  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.44-OCH.sub.3                                                    C.sub.2 H.sub.5                                                                    "    "   Br                            17  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.42-OH                                                           CH.sub.3                                                                           "    "   "                             18  C.sub.2 H.sub.5                                                                      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                                               "    "    "   "                             19  "      "                      "    "    "   Cl                            20  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.44-OH                                                           "    "    "   Br                            21  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.33-OH4-Cl                                                       "    "    "   Cl                            22  C.sub.3 H.sub.7                                                                      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                                               CH.sub.3                                                                           CH.sub.3                                                                           NO.sub.2                                                                          Br                            23  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.43-OH                                                           "    "    "   Cl                            24  C.sub.4 H.sub.9                                                                      CH.sub.2 CHOHCH.sub.2 C.sub.6 H.sub.5                                                                "    "    "   Br                            25  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CHCH.sub.2                                                           "    "    "   Br                            26  C.sub.2 H.sub.5                                                                      "                      "    "    "   Br                            27  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CCH                                                                  "    "    "   Br                            28  C.sub.2 H.sub.5                                                                      "                      "    "    "   Br                            29  C.sub.3 H.sub.7                                                                      "                      "    "    "   Br                            30  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                            "    "    "   Br                            31  "      "                      "    "    "   Cl                            32  "      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.44-Cl                                        "    "    "   Br                            33  C.sub.2 H.sub.5                                                                      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                            "    C.sub.2 H.sub.5                                                                    "   Br                            34  C.sub.3 H.sub.7                                                                      "                      "    CH.sub.3                                                                           "   Cl                            35  "      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.44-OCH.               sub.3                  "    "    "   Br                            36  "      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                            "    "    NO.sub.2                                                                          I                             37  CH.sub.3                                                                             CH.sub.2 CHOHC.sub.6 H.sub.5                                                                         "    "    "   Br                            38  "      CH(C.sub.6 H.sub.5)CH.sub.2 OH                                                                       "    "    "   Br                            39  "      CH.sub.2 CHOHC.sub.6 H.sub.5                                                                         "    "    "   Cl                            40  "      CH(C.sub.6 H.sub.5)CH.sub.2 OH                                                                       "    "    "   Cl                            41  C.sub.2 H.sub.5                                                                      "                      "    "    "   Br                            42  "      CH.sub.2 CHOHC.sub.6 H.sub.5                                                                         "    "    "   Br                            43  C.sub.3 H.sub.7                                                                      "                      "    "    "   Br                            44  "      CH(C.sub.6 H.sub.5)CH.sub.2 OH                                                                       "    "    "   Br                            45  CH.sub.3                                                                             CH.sub.2 CH.sub.2 OH   "    "    "   CN                            46  (CH.sub.2).sub.3 CH.sub.3                                                            "                      "    "    CN  "                             47  CH.sub.3                                                                             CH.sub.2 CH.sub.2OCONHC.sub.2 H.sub.5                                                                "    "    NO.sub.2                                                                          "                             48  "      CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                        "    "    CN  "                             49  C.sub.2 H.sub.5                                                                      CH.sub.2 CH.sub.2 OH   "    "    NO.sub.2                                                                          "                             50  C.sub.3 H.sub.7                                                                      CH.sub.2 CH.sub.2 OCONHC.sub.2 H.sub.5                                                               "    "    CN  "                             51  "      CH.sub.2 CH.sub.2 OH   "    "    "   "                             52  "      "                      C.sub.3 H.sub.7                                                                    "    "   "                             53  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.3  CH.sub.3                                                                           "    NO.sub.2                                                                          "                             54  "      "                      "    "    CN  "                             55  "      CH.sub.2 CHOHC.sub.2 H.sub.5                                                                         "    "    NO.sub.2                                                                          "                             56  C.sub.3 H.sub.7                                                                      "                      "    "    CN  "                             57  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                                               "    "    "   "                             58  "      "                      "    "    NO.sub.2                                                                          "                             59  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.44-Cl                                                           "    "    CN  "                             60  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.32,5-di-Cl                                                      "    "    "   "                             61  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.32,4-di-Cl                                                      "    "    "   "                             62         CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.43-OH                                                           "    "    "   "                             63  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.42-OH                                                           "    "    "   "                             64  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.44-CH.sub.3                                                     "    "    "   "                             65  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.43-CH.sub.3                                                     "    "    "   "                             66  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.32-CH.sub.34-Cl                                                 "    "    "   "                             67  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.44-OCH.sub.3                                                    "    "    "   "                             68  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.33-OH4Cl                                                        "    "    "   "                             69  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.43-OCH.sub.3                                                    "    "    "   "                             70  "      CH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                                                               C.sub.2 H.sub.5                                                                    "    "   "                             71  C.sub.2 H.sub.5                                                                      "                      CH.sub.3                                                                           "    NO.sub.2                                                                          "                             72  "      "                      "    "    CN  "                             73  C.sub.3 H.sub.7                                                                      "                      "    "    "   "                             74  CH.sub.3                                                                             "                      "    C.sub.2 H.sub.5                                                                    "   "                             75  "      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CHCH.sub.2                                                           "    CH.sub.3                                                                           NO.sub.2                                                                          "                             76  "      "                      "    "    CN  "                             77  C.sub.2 H.sub.5                                                                      "                      "    "    NO.sub.2                                                                          "                             78  "      "                      "    "    CN  "                             79  C.sub.3 H.sub.7                                                                      "                      "    "    NO.sub.2                                                                          "                             80  "      "                      C.sub.2 H.sub.5                                                                    "    CN  "                             81  C.sub.4 H.sub.9                                                                      "                      CH.sub.3                                                                           "    "   "                             82  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CCH                                                                  "    "    NO.sub.2                                                                          "                             83  C.sub.3 H.sub.7                                                                      "                      "    "    CN  "                             84  CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                            "    "    NO.sub.2                                                                          "                             85  "      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.44-OH                                        "    "    CN  "                             86  C.sub.2 H.sub.5                                                                      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           NO.sub.2                                                                          CN                            87  C.sub.3 H.sub.7                                                                      "                      CH.sub.3                                                                           "    CN  "                             88  CH.sub.3                                                                             CH.sub.2 CHOHC.sub.6 H.sub.5                                                                         "    "    NO.sub.2                                                                          "                             89  "      CH(C.sub.6 H.sub.5)CH.sub.2 OH                                                                       "    "    "   "                             90  "      "                      "    "    CN  "                             91  "      CH.sub.2 CHOHC.sub.6 H.sub.5                                                                         "    "    "   "                             92  C.sub.3 H.sub.7                                                                      "                      "    "    "   "                             93  "      CH(C.sub.6 H.sub.5)CH.sub.2 OH                                                                       "    "    "   "                             94  "      "                      "    "    NO.sub.2                                                                          "                             95  "      CH.sub.2 CHOHC.sub.6 H.sub.5                                                                         "    "    "   "                             96  C.sub.4 H.sub.9                                                                      "                      "    C.sub.2 H.sub.5                                                                    CN  "                             97  "      CH(C.sub.6 H.sub.5)CH.sub.2 OH                                                                       "    "    "   "                             98  C.sub.3 H.sub.7                                                                      CH.sub.2 CH(CH.sub.3)OCOCH.sub.3                                                                     "    CH.sub.3                                                                           "   "                             99  "      CH.sub.2 CH(CH.sub.3)OCOC.sub.2 H.sub.5                                                              "    "    "   "                             100 "      (CH.sub.2).sub.3OCOCH.sub.3                                                                          "    "    "   "                             101 CH.sub.3                                                                             CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                        "    "    NO.sub.2                                                                          Cl                            102 "      "                      "    "    "   Br                            103 "      CH.sub.2 CHOHCH.sub.2 OCH.sub.2 CHCHCl                                                               "    "    "   Cl                            __________________________________________________________________________

The dyestuffs of Example 3 to 103 dye polyester material a blue tone.(Examples 3 to 44 produce a navy blue tone) and have good fastnesses.

DYEING EXAMPLE (a) Production of a Dyeing Preparation

10 g of the dyestuff of Example 1, 9.3 g of sodium lignin sulphonate and25 ml of demineralised water are stirred in a 150 ml beaker with a twoplate stirrer at 150-200 revs. per minute. If a homogenous paste resultsthe rate of stirring is increased to a maximum of 1500-2000 revs. perminute whilst 156 g (=85 ml) of siliquarzite pearls (31-5/31-7 1:1) areadded until a viscous grindable surface layer results. The material isslowly ground whilst cooling in a continuous flowing water bath until afluid sample no longer produces a ring on a filter paper. The stirringis then reduced 500 revs. per minute and the mass is reacted with asolution of 9.3 g of sodium lignin sulphonate and 20 ml of demineralizedwater as a result of which the mass becomes slightly fluid. The mass ismixed well for 10 minutes, filtered through a glass filter flask G2 andrinsed with 300 ml of demineralised water.

The dispersion has a pH of 9.0-9.5 and is brought to pH of 6.5 by theaddition of a 10% phosphoric acid solution.

Finally the dispersion is dried and then finely pulverized in a mill.

Instead of the dyestuff of Example 1 any one of the dyestuffs ofExamples 2 to 103 may be used in an appropriate amount.

(b) Rapid Dyeing

5 Parts of a precleaned polyester web are immersed in a high temperaturedyeing bath in 100 parts of a dyebath heated to 70°, the 100 parts ofdyebath comprising 0.1 parts of the above-mentioned dyeing preparationof the dyestuff of Example 1 and 2 parts ammonium sulphate, the balancebeing water and the bath is brought to pH 5 by the addition of formicacid. The dyeing apparatus is then closed and is heated over 20 minutesto 130° and then maintained at this temperature for a further 20minutes. After cooling the polyester web is removed from the dyebath,rinsed, soaped, rinsed again and dried. A level deep blue dyeing resultswith good fastness properties. The remaining dyebath is practicallycolourless. Indeed when a sample is removed as soon as the dyebathreached 130° C. it has been found that the remaining dyebath containsabout 10% of the dyestuff.

Instead of the dyeing preparations of the dyestuff of Example 1 thedyeing preparations of a dyestuff of any one of Examples 2 to 103 may beused.

What is claimed is:
 1. A compound of the formula ##STR12## wherein R₂ ishalo,R₃ is C₁₋₄ alkyl, R₄ is methyl or ethyl, R₅ is C₁₋₈ alkyl, R₇ isphenyl; phenyl substituted by 1 or 2 substituents independently selectedfrom hydroxy, chloro, bromo, methyl and C₁₋₄ alkoxy; benzyl; benzylsubstituted by 1 or 2 substituents independently selected from hydroxy,chloro, bromo, methyl and C₁₋₄ alkoxy; allyl; allyl monosubstituted byhalo; or propyn-2-yl monosubstituted by halo, with the proviso that R₇may be allyl, allyl monosubstituted by halo or propyn-2-ylmonosubstituted by halo only when a is 0, and a is 0 or 1,wherein eachhalo is independently fluoro, chloro, bromo or iodo.
 2. A compoundaccording to claim 1 having the formula ##STR13## wherein R₂ is halo,R₅' is C₁₋₄ alkyl, R₇ ' is phenyl or phenyl substituted by 1 or 2substituents independently selected from hydroxy, chloro, bromo, methyland C₁₋₄ alkoxy, and a is 0 or
 1. 3. A compound according to claim 1having the formula ##STR14## wherein R_(2a) is chloro or bromo,R₃ isC₁₋₄ alkyl, R₄ is methyl or ethyl, and R₅ " is methyl or ethyl.
 4. Acompound according to claim 3 whereinR₃ is methyl, and R₄ is methyl. 5.The compound according to claim 4 having the formula ##STR15##
 6. Thecompound according to claim 4 having the formula ##STR16##
 7. Thecompound according to claim 4 having the formula ##STR17##
 8. Thecompound according to claim 4 having the formula ##STR18##
 9. Thecompound according to claim 2 having the formula ##STR19##
 10. Thecompound according to claim 2 having the formula ##STR20##
 11. Thecompound according to claim 2 having the formula ##STR21##
 12. Thecompound according to claim 2 having the formula ##STR22##
 13. Thecompound according to claim 2 having the formula ##STR23##
 14. Thecompound according to claim 1 having the formula ##STR24##
 15. Thecompound according to claim 1 having the formula ##STR25##
 16. Thecompound according to claim 1 having the formula ##STR26##
 17. Thecompound according to claim 1 having the formula ##STR27##